CN109244396A - The composite material of multi-walled carbon nanotube and Prussian blue similar object - Google Patents
The composite material of multi-walled carbon nanotube and Prussian blue similar object Download PDFInfo
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- CN109244396A CN109244396A CN201810995526.6A CN201810995526A CN109244396A CN 109244396 A CN109244396 A CN 109244396A CN 201810995526 A CN201810995526 A CN 201810995526A CN 109244396 A CN109244396 A CN 109244396A
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- walled carbon
- carbon nanotube
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to the composite material of a kind of multi-walled carbon nanotube and Prussian blue similar object, preparation includes the steps that following: aqueous dispersion and multi-walled carbon nanotube being added in deionized water and dissolved, mixed solution is obtained；Using potassium ferrocyanide/sodium ferrocyanide, sodium chloride and MnCl2 as the presoma for preparing Prussian blue similar object, after potassium ferrocyanide/sodium ferrocyanide is added in mixed solution, sodium chloride/sodium citrate is added in the mixed solution to the saturated solution for forming sodium chloride/sodium citrate, after MnCl2 is dissolved in deionized water, it is added dropwise in above-mentioned saturated solution and forms suspension；The solid material in suspension and drying are collected, the composite material of multi-walled carbon nanotube with Prussian blue similar object is obtained.Prepared multi-walled carbon nanotube is applied to sodium-ion battery anode with the composite material of Prussian blue similar object.
Description
Technical field
The present invention relates to a kind of using multi-walled carbon nanotube to the modification of Prussian blue similar object material, belong to sodium from
Sub- cell positive material field.
Background technique
Lithium ion battery have it is light-weight, capacity is big, operating temperature range is wide, self-discharge rate is low, non-environmental-pollution, without note
The features such as recalling effect, thus obtained commonly used.Current many digital equipments all use lithium ion battery as power supply, but
It is that lithium resource can not made short as the use of extensive energy-storage battery, causes cost increase.
Sodium element and elemental lithium are the element of same main group, have similar chemical property, in some applications can phase
Trans-substitution, and the storage capacity of sodium on earth is abundant, has oxidation-reduction potential more higher than lithium, in price, environmental protection and peace
Full property etc. is more advantageous.In terms of current research, the specific capacity of sodium-ion battery positive material is well below cathode material
Material, therefore developing high performance embedding sodium positive electrode is the key that improve sodium-ion battery specific energy and promote its application.
The Prussian blue similar object material of rich sodium form has a sodium reserves abundant, and this material have three-dimensional sodium from
The embedding de- channel of son can carry out intercalation/deintercalation for the biggish sodium ion of ionic radius.Its advantage mainly has at 3 points: (1) rigidity
Frame structure and open macrovoid, site guarantee that the biggish sodium ion of ionic radius can be reversible it is embedding de- without drawing
Play violent structural deformation；(2) because the redox reaction with bielectron, the theoretical capacity of Prussian are up to
170mAh g-1；(3) synthesis process is simple, nontoxic and at low cost so that this kind of material is suitable for large-scale production.But it because grinds
Study carefully the limitation of condition, it is also more to compare difference with its theoretical capacity for analog capacity in Prussia's at present.This is primarily due to Pu Lu
Scholar's analog materials conductive performance is poor, and the mass transfer impedance of electronics is larger, so that the cyclical stability of material and forthright again
It can decline.
In order to overcome the problems, such as this, there are two current main solutions: first is that by Prussian blue similar object and conduction
Polymer progress is compound, but is modified with carbon material Prussian blue similar object.Although stable circulation can be improved in the former
Property and high rate performance, but the addition of conducting polymer, the decline and the side reaction under high voltage that will cause whole specific capacity add
Play, in addition, the raising to material coulombic efficiency is not also fairly obvious.And carbon nanomaterial is due to light weight itself, and has very
Good electric conductivity, high stability, flexibility etc., allows sodium ion soon deviate from/be embedded in during charge and discharge, thus can
Not only to guarantee height ratio capacity but also improve its electric conductivity and ion transmission performance.
Summary of the invention
It modification is carried out to Prussian blue similar object with multi-walled carbon nanotube prepares one kind the object of the present invention is to provide a kind of
The multi-walled carbon nanotube method compound with Prussian blue similar object.The material is grown in multi wall by prussian blue nano particle in-situ
Constituted in carbon nanotube, preparation method process is simple, can volume production, which has good as sodium-ion battery positive material
Charge-discharge performance, high rate performance and stability, have a extensive future.Technical solution of the present invention passes through following steps reality
It is existing:
A kind of composite material of multi-walled carbon nanotube and Prussian blue similar object, Prussian blue similar object nano particle in situ
On multi-walled carbon nanotubes, wherein Prussian blue similar object nano particle diameter is in 200-400nm, multi-walled carbon nanotube is straight for growth
Diameter is 10-20nm, and multi-wall carbon nano-tube length of tube is 20-100 μm, the mass percent of multi-walled carbon nanotube in the composite material
Are as follows: 8%-10% obtains Prussian blue similar object material modification with multi-walled carbon nanotube, which is characterized in that including under
The step of column:
(1) aqueous dispersion and multi-walled carbon nanotube are added in deionized water and dissolve by, obtain mixed solution；
(2) is using one or both of potassium ferrocyanide and sodium ferrocyanide, sodium chloride and manganese chloride as preparing general Shandong
The presoma of scholar's indigo plant analog, with ferrocyanide and manganese chloride molar ratio 1:1, manganese chloride and multi-walled carbon nanotube mass ratio
(4.8~6.0): 1, sodium chloride and deionized water quality ratio (0.34~0.36): 1 meter adds potassium ferrocyanide/sodium ferrocyanide
Enter into mixed solution made from step (1), after mixing evenly, sodium chloride is added in the mixed solution and forms the full of sodium chloride
And solution；Manganese chloride is dissolved in deionized water, after mixing evenly, is added dropwise in above-mentioned saturated solution, suspension is formed；
(3) method of centrifugation collects the solid material in suspension, and being washed in product does not have the remaining sodium chloride to be
Only, the composite material of multi-walled carbon nanotube with Prussian blue similar object is obtained after drying.
The multi-walled carbon nanotube is applied to sodium-ion battery anode with the composite material of Prussian blue similar object.
Prepared multi-walled carbon nanotube is applied to sodium-ion battery anode with the composite material of Prussian blue similar object.
The invention has the following advantages that the present invention using raw material cheap and easy to get prepare multi-walled carbon nanotube with it is Prussian blue
The composite material of analog, low in cost, reaction process is simple, controllability is strong, and Prussian blue similar composition granule dispersibility is preferably.
Simultaneously the material structure it is uniform, pattern is excellent, has excellent performance, for sodium-ion battery anode have very high specific capacity with it is fabulous
Cycle performance, recycle 100 specific capacities for being still able to maintain 110mAh/g or more under the current density of 100mA/g, and
The specific capacity of 50mAh/g is still kept under the high current density of 500mA/g.
Detailed description of the invention
Fig. 1 is the SEM photograph for the multi-wall carbon nano-tube tube material that the embodiment of the present invention 1 is dispersed.From this view it is apparent that multi wall
The diameter and length of carbon nano-tube material.
Fig. 2 is that the multi-walled carbon nanotube that the embodiment of the present invention 1 obtains shines with the SEM of the composite material of Prussian blue similar object
Piece.From this view it is apparent that the Prussian blue similar object grown on multi-walled carbon nanotube nano particle.
Fig. 3 is that the multi-walled carbon nanotube that the embodiment of the present invention 1 obtains shines with the TEM of the composite material of Prussian blue similar object
Piece.From this view it is apparent that multi-walled carbon nanotube is completely embedded with Prussian blue similar object.
Fig. 4 is that the multi-walled carbon nanotube that the embodiment of the present invention 1 obtains shines with the TEM of the composite material of Prussian blue similar object
Piece.From this view it is apparent that Prussian blue similar object nano particle crystallinity is good.
Fig. 5 is the obtained multi-walled carbon nanotube of the embodiment of the present invention 1 and the XRD diagram of the composite material of Prussian blue similar object
Spectrum.
Fig. 6 is the obtained multi-walled carbon nanotube of the embodiment of the present invention 1 and the circulation of the composite material of Prussian blue similar object
Volt-ampere curve.From this view it is apparent that the composite material is with good stability.
Fig. 7 is the multi-walled carbon nanotube that is obtained using the embodiment of the present invention 1 and the composite material system of Prussian blue similar object
The charge-discharge performance figure of the sodium-ion battery anode obtained.
Fig. 8 is the multi-walled carbon nanotube that is obtained using the embodiment of the present invention 1 and the composite material system of Prussian blue similar object
The charge-discharge magnification performance map of the sodium-ion battery anode obtained.
Specific embodiment
Technology path of the invention is summarized first below.
The present invention is prepared for the composite material that a kind of multi-walled carbon nanotube modifies Prussian blue similar object, which is partial size
Uniform, finely dispersed Prussian blue similar object nano particle in situ is grown on multi-walled carbon nanotubes, wherein prussian blue
Like object nano particle diameter in 200-400nm, multi-wall carbon nano-tube pipe diameter is 10-20nm, and multi-wall carbon nano-tube length of tube is 20-
100 μm, the mass percent of multi-walled carbon nanotube in the composite material are as follows: 8%-10%.
The preparation method of the multi-walled carbon nanotube of above structure and the composite material of Prussian blue similar object, it is characterised in that
The following steps are included:
(1) is using TNWDIS as carbon nanotube aqueous dispersion, with dispersing agent and multi-walled carbon nanotube mass ratio for (0.2
~0.5): dispersing agent and multi-walled carbon nanotube are added in deionized water and dissolve by 1 meter, stirring wiring solution-forming, then ultrasound 20~
30min obtains mixed solution up to being uniformly mixed；
(2) is using potassium ferrocyanide/sodium ferrocyanide, sodium chloride and manganese chloride as before preparing Prussian blue similar object
Drive body, with ferrocyanide and manganese chloride molar ratio 1:1, manganese chloride and multi-walled carbon nanotube mass ratio (4.8~6.0): 1, chlorine
Change sodium and deionized water quality ratio (0.34~0.36): potassium ferrocyanide/sodium ferrocyanide is added to step (1) and is made by 1 meter
Mixed solution in, after mixing evenly, by sodium chloride be added in the mixed solution formed sodium chloride saturated solution, continue to stir
20~30min.Manganese chloride is dissolved in deionized water, after mixing evenly, is added dropwise in above-mentioned saturated solution, stirring for 24 hours, is formed
Suspension；
(3) method of centrifugation collects the solid material in suspension, and washing 3~4 times does not have remaining chlorine into product
Until changing sodium, is dried at being 60~120 DEG C in temperature, obtain the composite material of multi-walled carbon nanotube with Prussian blue similar object.
Particular content of the invention is described as follows combined with specific embodiments below:
Embodiment 1:
0.08g TNWDIS and 0.16g multi-walled carbon nanotube is weighed, mixture is dissolved in the deionized water of 100ml, with
The magnetic stirring apparatus of mixing speed 300r/min, stirring and dissolving wiring solution-forming, then again with power be 400W ultrasonic device ultrasound
20min forms mixed solution A.
Weigh 2.12g potassium ferrocyanide, 34g sodium chloride and 0.99g MnCl2, potassium ferrocyanide is added to mixed solution
In A, mixed solution B is formed after stirring 30min, sodium chloride is added in mixed solution B to the saturated solution C for forming sodium chloride, after
Continuous stirring 30min.By MnCl2It is dissolved in 100ml deionized water, after mixing evenly, is added dropwise in above-mentioned saturated solution C, is stirred
For 24 hours, suspension is formed.
The solid material in suspension is collected with the centrifuge of centrifugal speed 8000r/min, is washed with deionized water 3 times to production
Until there is no remaining sodium chloride in object, is dried at being 80 DEG C in temperature, obtain multi-walled carbon nanotube and Prussian blue similar object
Composite material, wherein Prussian blue similar object nano particle diameter 200-400nm, multi-wall carbon nano-tube pipe diameter is 10-20nm,
Multi-wall carbon nano-tube length of tube is 20-100 μm.
With obtained material, PVDF, conductive carbon black mass ratio is that 7:2:1 meter is applied to aluminium foil as anode, with 1M's
NaClO4As electrolyte, using sodium piece as cathode, half-cell is made, recycles 100 times and remains under the current density of 100mA/g
The specific capacity of 110mAh/g or more is kept, and still keeps the specific capacity of 50mAh/g, such as Fig. 7 under the high current density of 500mA/g
It is shown.
Embodiment 2:
0.07g TNWDIS and 0.16g multi-walled carbon nanotube is weighed, mixture is dissolved in the deionized water of 100ml, with
The magnetic stirring apparatus of mixing speed 300r/min, stirring and dissolving wiring solution-forming, then again with power be 400W ultrasonic device ultrasound
30min forms mixed solution A.
Weigh 2.12g potassium ferrocyanide, 34g sodium chloride and 0.99g MnCl2, potassium ferrocyanide is added to mixed solution
In A, mixed solution B is formed after stirring 30min, sodium chloride is added in mixed solution B to the saturated solution C for forming sodium chloride, after
Continuous stirring 30min.By MnCl2It is dissolved in 100ml deionized water, after mixing evenly, is added dropwise in above-mentioned saturated solution C, is stirred
For 24 hours, suspension is formed.
The solid material in suspension is collected with the centrifuge of centrifugal speed 8000r/min, is washed with deionized water 3 times to production
Until there is no remaining sodium chloride in object, is dried at being 100 DEG C in temperature, obtain multi-walled carbon nanotube and Prussian blue similar object
Composite material.
Embodiment 3:
0.08g TNWDIS and 0.16g multi-walled carbon nanotube is weighed, mixture is dissolved in the deionized water of 100ml, with
The magnetic stirring apparatus of mixing speed 300r/min, stirring and dissolving wiring solution-forming, then again with power be 400W ultrasonic device ultrasound
20min forms mixed solution A.
Weigh 2.65g potassium ferrocyanide, 34g sodium chloride and 1.24g MnCl2, potassium ferrocyanide is added to mixed solution
In A, mixed solution B is formed after stirring 30min, sodium chloride is added in mixed solution B to the saturated solution C for forming sodium chloride, after
Continuous stirring 30min.By MnCl2It is dissolved in 100ml deionized water, after mixing evenly, is added dropwise in above-mentioned saturated solution C, is stirred
For 24 hours, suspension is formed.
The solid material in suspension is collected with the centrifuge of centrifugal speed 8000r/min, is washed with deionized water 3 times to production
Until there is no remaining sodium chloride in object, is dried at being 80 DEG C in temperature, obtain multi-walled carbon nanotube and Prussian blue similar object
Composite material.
Embodiment 4:
0.08g TNWDIS and 0.16g multi-walled carbon nanotube is weighed, mixture is dissolved in the deionized water of 100ml, with
The magnetic stirring apparatus of mixing speed 300r/min, stirring and dissolving wiring solution-forming, then again with power be 400W ultrasonic device ultrasound
20min forms mixed solution A.
Weigh 2.36g potassium ferrocyanide, 34g sodium chloride and 1.10g MnCl2, potassium ferrocyanide is added to mixed solution
In A, mixed solution B is formed after stirring 30min, sodium chloride is added in mixed solution B to the saturated solution C for forming sodium chloride, after
Continuous stirring 30min.By MnCl2It is dissolved in 100ml deionized water, after mixing evenly, is added dropwise in above-mentioned saturated solution C, is stirred
For 24 hours, suspension is formed.
The solid material in suspension is collected with the centrifuge of centrifugal speed 8000r/min, is washed with deionized water 3 times to production
Until there is no remaining sodium chloride in object, is dried at being 100 DEG C in temperature, obtain multi-walled carbon nanotube and Prussian blue similar object
Composite material.
The present invention modifies Prussian blue similar object using multi-walled carbon nanotube, and growth in situ is general on the carbon nanotubes
Shandong scholar's indigo plant analog, the Material cladding is close, and preparation process is simple, and has superiority as sodium-ion battery positive material
Energy.
Claims (2)
1. the composite material of a kind of multi-walled carbon nanotube and Prussian blue similar object, Prussian blue similar object nano particle in situ is raw
It grows on multi-walled carbon nanotubes, wherein Prussian blue similar object nano particle diameter is in 200-400nm, multi-wall carbon nano-tube pipe diameter
For 10-20nm, multi-wall carbon nano-tube length of tube is 20-100 μm, the mass percent of multi-walled carbon nanotube in the composite material are as follows:
8%-10% obtains Prussian blue similar object material modification with multi-walled carbon nanotube.It is characterised in that it includes following
Step:
(1) aqueous dispersion and multi-walled carbon nanotube are added in deionized water and dissolve by, obtain mixed solution；
(2) is Prussian blue using one or both of potassium ferrocyanide and sodium ferrocyanide, sodium chloride and manganese chloride as preparing
The presoma of analog, with ferrocyanide and manganese chloride molar ratio 1:1, manganese chloride and multi-walled carbon nanotube mass ratio (4.8~
6.0): 1, sodium chloride and deionized water quality ratio (0.34~0.36): potassium ferrocyanide/sodium ferrocyanide is added to step by 1 meter
Suddenly in mixed solution made from (1), after mixing evenly, the saturation that formation sodium chloride in the mixed solution is added in sodium chloride is molten
Liquid；Manganese chloride is dissolved in deionized water, after mixing evenly, is added dropwise in above-mentioned saturated solution, suspension is formed；
(3) method of centrifugation collects the solid material in suspension, is washed in product until not having remaining sodium chloride,
The composite material of multi-walled carbon nanotube with Prussian blue similar object is obtained after drying.
2. multi-walled carbon nanotube prepared by claim 1 is applied to sodium-ion battery with the composite material of Prussian blue similar object
Anode.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110078096A (en) * | 2019-05-14 | 2019-08-02 | 上海汉行科技有限公司 | A kind of Prussian blue material and preparation method thereof |
| CN110540216A (en) * | 2019-08-13 | 2019-12-06 | 东华大学 | carbon-based Prussian blue analogue composite material and preparation method and application thereof |
| CN112479317A (en) * | 2020-12-01 | 2021-03-12 | 北京工业大学 | Preparation method and application of composite cathode integrating efficient in-situ hydrogen peroxide electrosynthesis and catalytic performance |
| CN112919496A (en) * | 2021-01-28 | 2021-06-08 | 中南大学 | High-dispersity Prussian blue nanoparticle/high-crystallization carbon composite material and preparation method thereof |
| CN113019450A (en) * | 2021-03-10 | 2021-06-25 | 南京大学 | Preparation method and application of carbon nanotube-encapsulated Prussian-like blue compound |
| CN114023938A (en) * | 2021-11-04 | 2022-02-08 | 山东零壹肆先进材料有限公司 | Positive electrode material and preparation method and application thereof |
| CN114203982A (en) * | 2021-11-01 | 2022-03-18 | 江苏大学 | Preparation method of vanadium-based Prussian blue analogue/carbon nanotube composite material and application of vanadium-based Prussian blue analogue/carbon nanotube composite material to water-based zinc ion battery anode |
| CN114436376A (en) * | 2022-01-31 | 2022-05-06 | 浙江佰辰低碳科技有限公司 | Electrode material for in-situ growth of Prussian blue analogue by taking MOF (Metal organic framework) derived carbon nanotube array as substrate and preparation method of electrode material |
| CN115117457A (en) * | 2022-08-26 | 2022-09-27 | 河南师范大学 | Preparation method of potassium ion full-cell device |
| WO2023184508A1 (en) * | 2022-04-01 | 2023-10-05 | 深圳先进技术研究院 | Carbon/berlin blue-like composite material and preparation method therefor and use thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110078096A (en) * | 2019-05-14 | 2019-08-02 | 上海汉行科技有限公司 | A kind of Prussian blue material and preparation method thereof |
| CN110540216A (en) * | 2019-08-13 | 2019-12-06 | 东华大学 | carbon-based Prussian blue analogue composite material and preparation method and application thereof |
| CN110540216B (en) * | 2019-08-13 | 2022-09-30 | 东华大学 | Carbon-based Prussian blue analogue composite material and preparation method and application thereof |
| CN112479317A (en) * | 2020-12-01 | 2021-03-12 | 北京工业大学 | Preparation method and application of composite cathode integrating efficient in-situ hydrogen peroxide electrosynthesis and catalytic performance |
| CN112919496A (en) * | 2021-01-28 | 2021-06-08 | 中南大学 | High-dispersity Prussian blue nanoparticle/high-crystallization carbon composite material and preparation method thereof |
| CN112919496B (en) * | 2021-01-28 | 2022-03-29 | 中南大学 | High-dispersity Prussian blue nanoparticle/high-crystallization carbon composite material and preparation method thereof |
| CN113019450A (en) * | 2021-03-10 | 2021-06-25 | 南京大学 | Preparation method and application of carbon nanotube-encapsulated Prussian-like blue compound |
| CN114203982A (en) * | 2021-11-01 | 2022-03-18 | 江苏大学 | Preparation method of vanadium-based Prussian blue analogue/carbon nanotube composite material and application of vanadium-based Prussian blue analogue/carbon nanotube composite material to water-based zinc ion battery anode |
| CN114023938A (en) * | 2021-11-04 | 2022-02-08 | 山东零壹肆先进材料有限公司 | Positive electrode material and preparation method and application thereof |
| CN114436376A (en) * | 2022-01-31 | 2022-05-06 | 浙江佰辰低碳科技有限公司 | Electrode material for in-situ growth of Prussian blue analogue by taking MOF (Metal organic framework) derived carbon nanotube array as substrate and preparation method of electrode material |
| WO2023184508A1 (en) * | 2022-04-01 | 2023-10-05 | 深圳先进技术研究院 | Carbon/berlin blue-like composite material and preparation method therefor and use thereof |
| CN115117457A (en) * | 2022-08-26 | 2022-09-27 | 河南师范大学 | Preparation method of potassium ion full-cell device |
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Application publication date: 20190118 |